CN112158923A - Preparation method of graphene-alumina porous composite material capable of being used as capacitive deionization electrode - Google Patents
Preparation method of graphene-alumina porous composite material capable of being used as capacitive deionization electrode Download PDFInfo
- Publication number
- CN112158923A CN112158923A CN202010974290.5A CN202010974290A CN112158923A CN 112158923 A CN112158923 A CN 112158923A CN 202010974290 A CN202010974290 A CN 202010974290A CN 112158923 A CN112158923 A CN 112158923A
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite material
- porous composite
- alumina
- capacitive deionization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a graphene-alumina porous composite material capable of being used as a capacitive deionization electrode, which is characterized in that a porous alumina material is used as a framework, a mixed slurry of graphene oxide dispersion liquid and ammonium bicarbonate or ammonium carbonate is used as a raw material, after vacuum coating, a heat treatment and thermal reduction process is adopted, and the prepared graphene-alumina porous composite material with high specific surface area, good pore structure and mechanical strength and good conductivity is used as an adsorption electrode of a capacitive deionization device and has excellent deionization performance on ions in various valence states in a solution. Moreover, the preparation method has the advantages of simple process, low cost, excellent performance, easily-controlled operation conditions and the like, and has wide application prospects in the fields of seawater desalination, salt-containing wastewater treatment and the like.
Description
Technical Field
The invention relates to the technical field of porous materials, in particular to a preparation method of a graphene-alumina porous composite material capable of being used as a capacitive deionization electrode.
Background
With the increasing global population and the continuous development of industry, the shortage of fresh water resources has become a significant problem facing the world. Desalination of sea water is one of the effective methods to alleviate the above problems. The desalination of sea water and brackish water requires high-efficiency ion removal (desalination) technology, and compared with the traditional desalination technology, the capacitance deionization technology has the outstanding technical advantages of high water resource utilization rate, low energy consumption, easy operation, easy regeneration of electrodes and the like, so that the capacitance deionization technology is paid much attention to the fields of desalination and the like.
Currently, for capacitive deionization technology, the structural performance characteristics of the electrode material are particularly critical to the desalination efficiency. Generally, the electrode material used for capacitive deionization should have the characteristics of good conductivity, large specific surface area, reasonable pore structure and the like. Graphene, as a novel advanced carbon material, has a large theoretical specific surface area (about 2630 m)2The specific surface area of the material is/g), the conductivity is high, and other excellent physical and chemical properties make the material show great application and development prospects in the technical field of capacitive deionization. However, in the current stage of graphene electrode materials, there are, for example: the stacking of sheets is easy to happen, so that the specific surface area of the sheets is reduced, the mechanical strength is low, the technical threshold of regulating and controlling the internal pore structure of the sheets and the preparation cost are high, and the like, thereby being not beneficial to the large-scale popularization and application of the graphene material in the capacitive deionization technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a graphene-alumina porous composite material which has simple process, low cost and easily controlled operation conditions and can be used as a capacitive deionization electrode.
The purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a graphene-alumina porous composite material capable of being used as a capacitive deionization electrode, which comprises the following steps:
(1) adding ammonium bicarbonate or ammonium carbonate into graphene oxide dispersion liquid with the concentration of 0.05-0.15 g/L for dissolving to form mixed slurry with the ammonium bicarbonate or ammonium carbonate content of 1-3 wt%;
(2) coating the mixed slurry on the inner and outer surfaces of the porous alumina sheet by adopting a vacuum coating process, then carrying out heat treatment, and repeating coating-heat treatment to obtain the graphene oxide-alumina porous composite material;
(3) and carrying out thermal reduction on the graphene oxide-aluminum oxide porous composite material in a hydrogen atmosphere to obtain the graphene oxide-aluminum oxide porous composite material which can be used as a capacitive deionization electrode.
Furthermore, the particle size of the graphene oxide is 50-200 nm. The most probable pore diameter of the porous alumina sheet is 1-2 mu m, and the porosity is 30-35%.
Further, the processing time of the vacuum coating in the step (2) is 20-30 min; heat treatment is carried out for 2-3 h at the temperature of 95-100 ℃; the number of times of repeating the coating-heat treatment is 5 to 10. The temperature of the thermal reduction treatment in the step (3) is 900-1000 ℃, and the treatment time is 24-36 h. And (4) the resistance of the thermally reduced graphene in the step (3) is 150-200 omega.
The graphene-alumina porous composite material prepared by the invention is subjected to silver screen coating on one surface, two pieces of the graphene-alumina porous composite material are respectively marked as a positive electrode and a negative electrode and are connected with a lead to form the graphene-alumina porous composite electrode, and the graphene-alumina porous composite electrode is suitable for a direct-current power supply with the voltage of 0.6-1.2V.
The invention has the following beneficial effects:
(1) the graphene-alumina porous composite material is prepared by taking a porous alumina material as a framework and taking mixed slurry of graphene oxide dispersion liquid and ammonium bicarbonate or ammonium carbonate as raw materials through a vacuum coating-heat treatment-thermal reduction process, and has a high specific surface area (260-300 m)2The conductive polymer has the advantages of a good pore structure (porosity of 30-35 percent), a good mechanical strength (flexural strength of 23-28 MPa), good conductivity (resistance of 150-200 omega) and low preparation cost, and has excellent effect on ions of multiple valence states in a solution when being used as an adsorption electrode of a capacitive deionization deviceGood removal performance (for Na)+、K+、Ca2+The adsorption rates of (a) are 8 to 35%, 6 to 30%, and 4.5 to 10%, respectively).
(2) The preparation method has the advantages of simple process, low cost, excellent performance, easily controlled operation conditions and the like, and has wide application prospect in the fields of seawater desalination, salt-containing wastewater treatment and the like.
Drawings
The invention will now be described in further detail with reference to the following examples and the accompanying drawings:
fig. 1 is a microscopic structural view of a graphene-alumina porous composite material prepared by an example of the present invention;
fig. 2 is a schematic structural diagram of an electrode assembled by the graphene-alumina porous composite material prepared in the embodiment of the present invention.
Detailed Description
The first embodiment is as follows:
the embodiment of the invention provides a preparation method of a graphene-alumina porous composite material capable of being used as a capacitive deionization electrode, which comprises the following steps:
(1) adding ammonium carbonate into graphene oxide dispersion liquid with the concentration of 0.05g/L (the particle size of graphene oxide is 50nm) to dissolve the ammonium carbonate to form mixed slurry with the ammonium carbonate content of 1 wt%;
(2) completely immersing a porous alumina sheet with most probable pore diameter of 1 mu m and porosity of 30% into the mixed slurry, treating in-0.9 bar vacuum for 30min to enable graphene oxide and ammonium carbonate to be uniformly combined on the surface of alumina, and then carrying out heat treatment at 100 ℃ for 2h to enable the graphene oxide and the ammonium carbonate to be firmly combined; repeating the coating-heat treatment process for 10 times to obtain a firmly combined graphene oxide-aluminum oxide porous composite material;
(3) the graphene oxide-alumina porous composite material is subjected to thermal reduction treatment after being slowly heated to 1000 ℃ for 36 hours in a hydrogen atmosphere, and the graphene oxide is reduced to graphene with the resistance of 150 omega, so that the graphene oxide-alumina porous composite material capable of being used as a capacitive deionization electrode is obtained.
Example two:
the embodiment of the invention provides a preparation method of a graphene-alumina porous composite material capable of being used as a capacitive deionization electrode, which comprises the following steps:
(1) adding ammonium bicarbonate into graphene oxide dispersion liquid with the concentration of 0.15g/L (the particle size of graphene oxide is 200nm) to dissolve the ammonium bicarbonate to form mixed slurry with the ammonium bicarbonate content of 3 wt%;
(2) completely immersing a porous alumina sheet with most probable pore diameter of 2 mu m and porosity of 35% into the mixed slurry, treating in-0.9 bar vacuum for 20min to enable graphene oxide and ammonium bicarbonate to be uniformly combined on the surface of alumina, and then carrying out heat treatment at 95 ℃ for 3h to enable the graphene oxide and the ammonium bicarbonate to be firmly combined; repeating the coating-heat treatment process for 5 times to obtain a firmly combined graphene oxide-aluminum oxide porous composite material;
(3) the graphene oxide-alumina porous composite material is subjected to thermal reduction treatment by slowly heating to 900 ℃ for 24 hours in a hydrogen atmosphere, and the graphene oxide is reduced to graphene with the resistance of 200 omega, so that the graphene oxide-alumina porous composite material capable of being used as a capacitive deionization electrode is obtained.
Example three:
the embodiment of the invention provides a preparation method of a graphene-alumina porous composite material capable of being used as a capacitive deionization electrode, which comprises the following steps:
(1) adding ammonium bicarbonate into graphene oxide dispersion liquid with the concentration of 0.10g/L (the particle size of graphene oxide is 100nm) for dissolving to form mixed slurry with the ammonium bicarbonate content of 2 wt%;
(2) completely immersing a porous alumina sheet with most probable pore diameter of 1.5 mu m and porosity of 32% into the mixed slurry, treating in-0.9 bar vacuum for 30min to ensure that the graphene oxide and the ammonium bicarbonate are uniformly combined on the surface of the alumina, and then carrying out heat treatment at 100 ℃ for 2h to ensure that the combination is firm; repeating the coating-heat treatment process for 8 times to obtain a firmly combined graphene oxide-aluminum oxide porous composite material;
(3) the graphene oxide-alumina porous composite material is subjected to thermal reduction treatment by slowly heating to 950 ℃ for 30 hours in a hydrogen atmosphere, and the graphene oxide is reduced to graphene with the resistance of 180 ohms, so that the graphene oxide-alumina porous composite material capable of being used as a capacitive deionization electrode is obtained.
As shown in fig. 1, in the graphene-alumina porous composite material prepared in the embodiment of the present invention, graphene is uniformly coated on the surfaces of all alumina particles. The three-point bending method is adopted to test the flexural strength, and the Archimedes method and the dynamic nitrogen adsorption method are respectively adopted to measure the porosity and the specific surface area, and the test results are shown in Table 1.
Table 1 performance index of graphene-alumina porous composite material prepared in the embodiment of the present invention
As shown in fig. 2, a graphene-alumina porous composite material prepared in the embodiment of the present invention is subjected to silver screen coating on one surface, two sheets are respectively marked as a positive electrode and a negative electrode and connected to a lead to form a graphene-alumina porous composite electrode (i.e., an adsorption electrode), the adsorption electrode is connected to an external power supply with a voltage of 0.6-1.2V, and 100-1000 mg/L NaCl, KCl, CaCl, and CaCl is applied2The solution was subjected to ion adsorption, and the performance index thereof is shown in Table 2.
Table 2 adsorption performance of the graphene-alumina porous composite electrode formed in the example of the present invention
*The solution is NaCl solution, KCl solution, CaCl2And (3) solution.
Claims (6)
1. A preparation method of a graphene-alumina porous composite material capable of being used as a capacitive deionization electrode is characterized by comprising the following steps: the method comprises the following steps:
(1) adding ammonium bicarbonate or ammonium carbonate into graphene oxide dispersion liquid with the concentration of 0.05-0.15 g/L for dissolving to form mixed slurry with the ammonium bicarbonate or ammonium carbonate content of 1-3 wt%;
(2) coating the mixed slurry on the inner and outer surfaces of the porous alumina sheet by adopting a vacuum coating process, then carrying out heat treatment, and repeating coating-heat treatment to obtain the graphene oxide-alumina porous composite material;
(3) and carrying out thermal reduction on the graphene oxide-aluminum oxide porous composite material in a hydrogen atmosphere to obtain the graphene oxide-aluminum oxide porous composite material which can be used as a capacitive deionization electrode.
2. The method for preparing the graphene-alumina porous composite material used as the capacitive deionization electrode according to claim 1, wherein: the particle size of the graphene oxide is 50-200 nm.
3. The method for preparing the graphene-alumina porous composite material used as the capacitive deionization electrode according to claim 1, wherein: the most probable pore diameter of the porous alumina sheet is 1-2 mu m, and the porosity is 30-35%.
4. The method for preparing the graphene-alumina porous composite material used as the capacitive deionization electrode according to claim 1, wherein: the processing time of the vacuum coating in the step (2) is 20-30 min; heat treatment is carried out for 2-3 h at the temperature of 95-100 ℃; the number of times of repeating the coating-heat treatment is 5 to 10.
5. The method for preparing the graphene-alumina porous composite material used as the capacitive deionization electrode according to claim 1, wherein: the temperature of the thermal reduction treatment in the step (3) is 900-1000 ℃, and the treatment time is 24-36 h.
6. The method for preparing the graphene-alumina porous composite material used as the capacitive deionization electrode according to claim 1, wherein: and (4) the resistance of the thermally reduced graphene in the step (3) is 150-200 omega.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010974290.5A CN112158923B (en) | 2020-09-16 | 2020-09-16 | Preparation method of graphene-alumina porous composite material capable of being used as capacitive deionization electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010974290.5A CN112158923B (en) | 2020-09-16 | 2020-09-16 | Preparation method of graphene-alumina porous composite material capable of being used as capacitive deionization electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112158923A true CN112158923A (en) | 2021-01-01 |
| CN112158923B CN112158923B (en) | 2022-10-25 |
Family
ID=73858045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010974290.5A Active CN112158923B (en) | 2020-09-16 | 2020-09-16 | Preparation method of graphene-alumina porous composite material capable of being used as capacitive deionization electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112158923B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023057824A1 (en) * | 2021-10-07 | 2023-04-13 | University Of Colombo | Composition for dye removal from an aqueous system and methods of preparation thereof |
| GB2623155A (en) * | 2022-08-03 | 2024-04-10 | Politechnika Lodzka | A sieve electrode for separating ions |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757036A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of porous graphene |
| CN103943380A (en) * | 2014-04-24 | 2014-07-23 | 陆艾珍 | Carbon porous electrode preparing method |
| CN105879707A (en) * | 2016-07-03 | 2016-08-24 | 景德镇陶瓷大学 | Reduced-oxidized graphene modified ceramic membrane with efficient ion rejection performance |
| CN107399792A (en) * | 2017-08-16 | 2017-11-28 | 北京理工大学 | A kind of high carrying capacity electric capacity demineralizer for including renewable three-diemsnional electrode |
| CN108117410A (en) * | 2017-12-19 | 2018-06-05 | 华中科技大学 | A kind of three-dimensional porous ceramics-graphene block composite material and preparation method thereof |
| KR102075911B1 (en) * | 2018-10-16 | 2020-02-12 | 한국생산기술연구원 | Composite sensor and manufacturing method thereof |
-
2020
- 2020-09-16 CN CN202010974290.5A patent/CN112158923B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757036A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of porous graphene |
| CN103943380A (en) * | 2014-04-24 | 2014-07-23 | 陆艾珍 | Carbon porous electrode preparing method |
| CN105879707A (en) * | 2016-07-03 | 2016-08-24 | 景德镇陶瓷大学 | Reduced-oxidized graphene modified ceramic membrane with efficient ion rejection performance |
| CN107399792A (en) * | 2017-08-16 | 2017-11-28 | 北京理工大学 | A kind of high carrying capacity electric capacity demineralizer for including renewable three-diemsnional electrode |
| CN108117410A (en) * | 2017-12-19 | 2018-06-05 | 华中科技大学 | A kind of three-dimensional porous ceramics-graphene block composite material and preparation method thereof |
| KR102075911B1 (en) * | 2018-10-16 | 2020-02-12 | 한국생산기술연구원 | Composite sensor and manufacturing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023057824A1 (en) * | 2021-10-07 | 2023-04-13 | University Of Colombo | Composition for dye removal from an aqueous system and methods of preparation thereof |
| GB2623155A (en) * | 2022-08-03 | 2024-04-10 | Politechnika Lodzka | A sieve electrode for separating ions |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112158923B (en) | 2022-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Frontiers of carbon materials as capacitive deionization electrodes | |
| CN105780364B (en) | A kind of method for preparing ultramicropore flexibility carbon cloth and products thereof and application | |
| CN110670107B (en) | Titanium carbide nanosheet/carbon nanotube electromagnetic shielding film and preparation method thereof | |
| CN109603596B (en) | Photo-thermal seawater desalination membrane made of metal organic framework material | |
| CN112158923B (en) | Preparation method of graphene-alumina porous composite material capable of being used as capacitive deionization electrode | |
| CN108187606B (en) | Conductive titanium lithium ion sieve and preparation method thereof | |
| CN107601501A (en) | A kind of preparation method and applications of biomass-based porous carbon | |
| CN111600000B (en) | Carbon nanotube graphene/silicon carbon composite material, and preparation method and application thereof | |
| CN112898610B (en) | Flexible metal-organic framework/gelatin composite film and preparation method and application thereof | |
| CN109734158A (en) | A kind of nitrogen, sulphur codope porous carbon sheet capacitive desalination electrode material and its preparation and application | |
| CN102738477B (en) | The ordering single electrodes of proton conductors and membrane electrode and preparation method is tieed up based on 3 | |
| CN108383112A (en) | A kind of high heat graphene heating film and preparation method thereof | |
| Liu et al. | Electrosorption performance on graphene-based materials: A review | |
| CN108796560B (en) | Preparation method of activated carbon loaded nano zero-valent iron composite material | |
| CN102698741B (en) | Method for preparing grapheme platinum nanocomposite material by using argon plasma | |
| CN102738478B (en) | Three-dimensional proton conductor based single electrode and fuel cell membrane electrode as well as preparation methods | |
| CN106981650A (en) | A kind of preparation method of nanoscale bismuth with elementary | |
| CN110120547B (en) | Preparation method of electrolyte membrane for all-solid-state lithium ion battery and electrolyte membrane | |
| CN104577135A (en) | Preparation method of three-dimensional silver mesh | |
| CN107104001A (en) | A kind of method for improving specific capacitance in graphenic surface adsorption of hydrolyzation polyimide molecule | |
| CN116936751A (en) | Ultrathin high-efficiency graphene composite membrane-based lithium carrier and application of lithium metal battery thereof | |
| CN105932255A (en) | Preparation method of graphene/lithium iron phosphate composite material | |
| CN109354014A (en) | A kind of graphitized carbon quantum dot and preparation method thereof | |
| CN107665996A (en) | Three-dimensional porous nickel doughnut electrode material, preparation method and the battery based on the electrode | |
| CN108615887B (en) | Preparation method of sodium ion battery foam graphene negative electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |